Facile preparation of a new BINAP-based building block, 5,5'-diiodoBINAP, and its synthetic application.

[reaction: see text] Bis(pyridine)iodonium tetrafluoroborate was successfully used for regioselective iodination of BINAP dioxide to give 5,5'-diiodoBINAP dioxide in an excellent yield of 92%, with no observed formation of 4,4'-diiodoBINAP dioxide. A Sonogashira cross-coupling reaction with 5,5'-diiodoBINAP dioxide gave the desired bis(trimethylsilylethynyl) product in 86% yield. The resulting 5,5'-disubstituted BINAP dioxides were reduced to the corresponding phosphines, which were used as chiral ligands for rhodium-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone to give 3-phenylcyclohexanone in excellent yield with high enantioselectivity.

An alternate route for the synthesis of hybrid mesoporous organosilica with crystal-like pore walls from allylorganosilane precursors.

The bridged allylorganosilanes 1,4-bis(diallylethoxysilyl)benzene and 1,4-bis(triallylsilyl)benzene are presented as new precursors for the surfactant-assisted synthesis of ordered mesoporous organosilica with pore walls having crystal-like molecular-scale periodicity. This approach provides a new route to the formation of periodic mesostructures with crystal-like pore walls. The synthesis method presented is applicable to the preparation of mesoporous organosilica with bulky organic groups, the precursors of which are typically impossible to obtain in high purity.